Potassium Formate → 6-(2-Dodecylsulfonylbutyryl)amino-5-fluoro-benzoxazol-2-one

HRID 1058212

反応式

HRID 1058212 の反応式
[F:1][C:2]1[C:3]([N+:12]([O-])=O)=[CH:4][C:5]2[O:9][C:8](=[O:10])[NH:7][C:6]=2[CH:11]=1.C([O-])=O.[K+].NC1C(F)=CC2NC(=O)OC=2C=1.[CH2:31]([S:43]([CH:46]([CH2:50][CH3:51])[C:47](Cl)=[O:48])(=[O:45])=[O:44])[CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42]>O.C(OCCC)(=O)C.[Pd].C(O)(C)C>[CH2:31]([S:43]([CH:46]([CH2:50][CH3:51])[C:47]([NH:12][C:3]1[C:2]([F:1])=[CH:11][C:6]2[NH:7][C:8](=[O:10])[O:9][C:5]=2[CH:4]=1)=[O:48])(=[O:45])=[O:44])[CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42]

参加物

9

反応物 4

HCID 2735122Potassium FormateHCID 112178355-Fluoro-6-nitro-2,3-dihydro-1,3-benzoxazol-2-oneHCID 114732302-Dodecylsulfonyl-butyryl chlorideHCID 156759596-Amino-5-fluoro-2,3-dihydro-1,3-benzoxazol-2-one

生成物 1

HCID 112599646-(2-Dodecylsulfonylbutyryl)amino-5-fluoro-benzoxazol-2-one収率 79.1%

試薬・触媒・溶媒 4

HCID 23938Palladium触媒HCID 962Water溶媒3 回HCID 3776Isopropanol溶媒HCID 7997Propyl Acetate溶媒3 回

実験手順

In a 250-ml flask, place 9.9 g (0.05 m) of 5-fluoro-6-nitro-benzoxazol-2-one (2a), 40 ml of isopropyl alcohol and 20 ml of propyl acetate, and 0.4 g 5% Pd/C with 1.5 ml of water. Add 16.8 g (0.2 m) of potassium formate in 20 ml of water, and stir the mixture vigorously at 55°-60° C. for 4 hrs. Keep strictly inert nitrogen atmosphere throughout the reaction. Take a TLC to confirm completeness of reaction. Cool the reaction mixture containing 6-amino-5-fluoro-benzoxazol-2-one (3a, X=F) to 40° C. under nitrogen, and add 40 ml of propyl acetate and a solution of 18.8 g (0.05 m×1.05 @95%) of 2-dodecylsulfonyl-butyryl chloride (R′COZ; R′=1-dodecylsulfonylpropyl and Z=Cl) in 60 ml of propyl acetate keeping the temperature at 40°-45° C. over 15 min. Stir the reaction mixture at 40° C. for 30 min. Add 60 ml of water and filter off catalyst and wash it with 60 ml of propyl acetate and 60 ml of water. Separate propyl acetate solution, wash with 120 ml of 1N HCl, and concentrate under a reduced pressure to a thick slurry. Cool the slurry in an ice-water bath for 2 hrs. Collect solid, wash with chilled propyl acetate and heptane, and dry in a vacuum oven to give 18.6 g (79%) of 6-(2-dodecylsulfonylbutyryl)amino-5-fluoro-benzoxazol-2-one (Formula I, Y=X=F and R′=1-dodecylsulfonylpropyl) as off-white solids.

後処理

  1. customthroughout the reaction
  2. customcompleteness of reaction
  3. temperatureCool the reaction mixture
  4. stirringStir the reaction mixture at 40° C. for 30 min
  5. filtrationfilter off catalyst
  6. washwash it with 60 ml of propyl acetate and 60 ml of water
  7. washSeparate propyl acetate solution, wash with 120 ml of 1N HCl
  8. concentrationconcentrate under a reduced pressure to a thick slurry
  9. temperatureCool the slurry in an ice-water bath for 2 hrs
  10. customCollect solid
  11. washwash with chilled propyl acetate and heptane
  12. customdry in a vacuum oven

出典と根拠

ORDレコード
ord-65ad409e92064a2d9b86d2bdfa7ae3a8
出典データセット
uspto-grants-2003_02
特許番号
US06515176B1

関連ノート

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